CN105602181A - Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof - Google Patents
Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof Download PDFInfo
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- CN105602181A CN105602181A CN201511008444.0A CN201511008444A CN105602181A CN 105602181 A CN105602181 A CN 105602181A CN 201511008444 A CN201511008444 A CN 201511008444A CN 105602181 A CN105602181 A CN 105602181A
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Abstract
The invention discloses a carbon nanotube modified thermoplastic elastomer composite material with a solvent resistance and a preparing method thereof. A modified thermoplastic elastomer and carbon nanotubes are dissolved in an organic solvent, heated, stirred uniformly and molded at high temperature to obtain the carbon nanotube modified thermoplastic elastomer composite material with the solvent resistance. According to percent by weight, the carbon nanotube modified thermoplastic elastomer composite material with the solvent resistance is prepared from 90-99% of modified thermoplastic elastomer and 1-10% of carbon nanotubes. The carbon nanotube modified thermoplastic elastomer composite material with the solvent resistance has excellent mechanical properties and solvent resistance, is of a crosslink structure and cannot be dissolved at normal temperature and keeps a remolding characteristic at high temperature. The carbon nanotubes can be recycled separately as per required, and the solution of the dissolved composite material is centrifuged and heated to obtain the modified thermoplastic elastomer and the carbon nanotubes respectively.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, the present invention relates to a kind of carbon with solvent resistance and receiveMitron modified thermoplastic elastomer composite and preparation method thereof.
Background technology
Styrene series thermoplastic elastomer (is called again styrene block copolymer StyreneicBlockCopolymers, letterClaim SBCs), be world wide production maximum, a kind of thermoplastic elastomer (TPE) the most similar to rubber performance at present.
SBS styrene analog thermoplastic elastomer is that output maximum (accounting for more than 70%) in SBCs, cost are minimum, applicationA wider kind, is the triblock copolymer taking styrene, butadiene as monomer, has the spy of plastics and rubber concurrentlyProperty, be called as " third generation synthetic rubber ". Similar to butadiene-styrene rubber, SBS can contact with water, weak acid, alkali etc., toolThe characteristics such as have good hot strength, skin-friction coefficient is large, and cryogenic property is good, and electrical property is good, good processability,Become the thermoplastic elastomer (TPE) of current consumption figure maximum. Styrene analog thermoplastic elastomer SBC (TPE-S) is due to PB phasePhysical crosslinking has the characteristic of plastics and rubber simultaneously, is therefore called as " third generation synthetic rubber "; On the one hand, SBC(TPE-S) to have hot strength good for material, and skin-friction coefficient is large, and cryogenic property is good, the good and processing characteristics of electrical propertyGood, when use, without the feature such as crosslinked, be the thermoplastic elastomer (TPE) of current consumption figure maximum, but then, SBC(TPE-S) the such as SBS (polystyrene-butadiene-styrene) in material and SIS (polystyrene-different propylene-styrene) etc.There is the shortcomings such as intensity is lower, easy aging. Although thermoplastic elastomer (TPE) is being plastic use without crosslinked in the situation that,This non-crosslinked structure, the solvent resistance that also makes material a little less than, can be by organic solvent dissolution.
Summary of the invention
In order to overcome above-mentioned problem, the object of the present invention is to provide a kind of CNT with solvent resistance to changeProperty thermoplastic elastomer composite material and preparation method thereof. Preparation method of the present invention is simple, the carbon nano-tube modification obtainingThermoplastic elastomer composite material, under the thermoplastic prerequisite of reserved materials, mechanical property excellence, solvent resistance is good,And can recycle.
Technical solution of the present invention is specific as follows.
The invention provides a kind of carbon nano-tube modification thermoplastic elastomer composite material with solvent resistance, this is compoundMaterial is composited by modified thermoplastic elastomer and CNT, percentage meter by weight, the modification in compositeThermoplastic elastomer (TPE) accounts for 90-99%; CNT accounts for 1-10%; Wherein: described modified thermoplastic elastomer is that furans connectsThe unsaturated thermoplastic elastomer (TPE) of branch modification.
In the present invention, unsaturated thermoplastic elastomer (TPE) is the styrene analog thermoplastic elastomer that molecule includes unsaturated double-bond.Preferably, be SBS (polystyrene-butadiene-styrene) or SIS (polystyrene-different propylene-styrene).
In the present invention, in modified thermoplastic elastomer, the graft ratio of furans is in modified thermoplastic elastomer, to repeat listThe ratio of the molal quantity of carbon-carbon double bond in unsaturated thermoplastic elastomer (TPE) before molal quantity summation and the modification of unit; Its graftingRatio is 5-50%; Preferably, graft ratio is 10%～30%. Carbon in unsaturated thermoplastic elastomer (TPE) before modificationThe molal quantity of the two keys of carbon, in the raw material that can provide according to producer, various structural formula cubages obtain.
In the present invention, the unsaturated process for preparation of thermoplastic elastomer of furans graft modification is as follows: will contain furans knotThe sulfhydryl compound of structure and unsaturated thermoplastic elastomer (TPE) are dissolved in organic solvent, add light trigger, stirAfter, under the condition of ultraviolet lighting, complete graft reaction.
In the present invention, CNT is SWCN or multi-walled carbon nano-tubes.
The present invention also provides a kind of above-mentioned carbon nano-tube modification thermoplastic elastomer composite material with solvent resistancePreparation method, it is by being dispersed in modified thermoplastic elastomer and CNT dissolving in organic solvent, and heating, stirsAfter mixing evenly, high temperature film forming prepares; The wherein furans percent grafting of modified thermoplastic elastomer and adding of CNTDosage can be set as required, and then designs as required the mechanicalness of this composite of regulation and control. Preferably, obtainIn composite, percentage meter by weight, modified thermoplastic elastomer accounts for 90-99%; CNT accounts for 1-10%.
In above-mentioned preparation method, described organic solvent is selected from benzene, dimethylbenzene, toluene, alcohols, chloroform, dichloromethaneAlkane, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide (DMSO), N, N '-dimethyl formamide, N, in N '-dimethylacetylamide or ketoneAny.
In above-mentioned preparation method, it is characterized in that, heating-up temperature is 60-130 DEG C.
The carbon nano-tube modification thermoplastic elastomer composite material with solvent resistance in the present invention can be reinvented, reclaimUtilize. In the present invention by unsaturated modification thermoplastic elastomer (TPE) and carbon nanotube dispersed in solvent, in the condition of heatingUnder, this system is carried out Di Ersi – Alder reaction, makes molecular chemistry crosslinked, obtains the solvent resistance that has of reversible crosslinkThe unsaturated thermoplastic elastomer composite material of carbon nano-tube modification of energy. Material after crosslinked has excellent mechanical propertyAnd solvent resistance, be again that heat is reversible because this is crosslinked, such system can heating condition be issued to reclaim andThe effect of reinventing; It passes through by the carbon nano-tube modification thermoplastic elastomer composite material after moulding, 130-180 DEG C of temperatureDegree is lower to be separated crosslinkedly, and high temperature film forming again while hot, can reach the object of post forming; It passes through the material after moulding,After at 130-180 DEG C of temperature, solution is cross-linked, while hot by hot solution centrifugal treating, filtrate partial concentration obtains modified thermoplasticElastomer, filter residue part is CNT. Above-mentionedly reinvent and reclaim carbon nano-tube modification thermoplastic elastomer (TPE) composite woodWhen material, solvent is dimethylbenzene, dichloro-benzenes, trichloro-benzenes etc.
Beneficial effect of the present invention is: preparation method of the present invention is simple, the carbon nano-tube modification thermoplastic elastic obtainingComposite material, under the thermoplastic prerequisite of reserved materials, mechanical property excellence, solvent resistance is good, and can returnReceive and utilize.
Brief description of the drawings
Fig. 1 is the equation with the SBS after furan modified (polystyrene-butadiene-styrene) and CNT reaction.
Fig. 2 is that SBS (polystyrene-butadiene-styrene) that in embodiment 1, different furans graft ratio are 20% is from differentThe stress-strain curve of the composite of CNT addition, CNT adds content and is respectively 1%, 2.5%, 5%,7.5% and 10%.
Fig. 3 is that SBS (polystyrene-butadiene-styrene) that in embodiment 2, different furans graft ratio are 30% is from differentThe stress-strain curve of the composite of CNT addition, CNT adds content and is respectively 1%, 2.5%, 5%,7.5% and 10%.
Fig. 4 is that the furans percent grafting of three repetition moulding in embodiment 3 is 20%, and what CNT addition was 10% answersCondensation material stress-strain curve.
Detailed description of the invention
According to specific embodiment, technical scheme of the present invention is described further below. Protection scope of the present invention be not limited toLower embodiment, enumerates these examples and does not only limit the present invention in any way for exemplary purpose.
Embodiment 1
By the elastomeric material after furans graft modification (SBS that is 20% by furans grafting amount) and CNT herein(content is respectively 1%, 2.5%, 5%, 7.5% and 10%) dissolved and is dispersed in solvent, after heating is uniformly dispersed,100 DEG C of film forming. Fig. 1 is with the SBS after furan modified (polystyrene-butadiene-styrene) and CNT reactionEquation.
Fig. 2 be SBS that in embodiment 1, furans graft ratio is 20% from the composite of different CNT additions shouldForce-strain curve figure, CNT adds content and is respectively 1%, 2.5%, 5%, 7.5% and 10%.
The SBS that table 1 is 20% for furans graft ratio in embodiment, carbon pipe grafting amount is 1%, 2.5%, 5%, 7.5%Elongation at break and fracture strength with the modified SBS of 10% reversible crosslink.
Table 1
| Carbon pipe addition (%) | 0 | 1 | 2.5 | 5 | 7.5 | 10 |
| Fracture strength (MPa) | 3.26 | 16.47 | 18.54 | 17.81 | 15.32 | 17.63 |
| Elongation at break (%) | 1064.9 | 889.2 | 829.4 | 691.8 | 601.3 | 605.8 |
Embodiment 2
By the elastomeric material after furans graft modification (SBS that is 30% by furans grafting amount) and CNT herein(content is respectively 1%, 2.5%, 5%, 7.5% and 10%) dissolved and is dispersed in solvent, after heating is uniformly dispersed,100 DEG C of film forming.
Fig. 3 is that SBS (polystyrene-butadiene-styrene) that in embodiment 2, different furans graft ratio are 30% is from differentThe stress-strain curve of the composite of CNT addition, CNT adds content and is respectively 1%, 2.5%, 5%,7.5% and 10%.
The SBS that table 2 is 30% for furans graft ratio in embodiment, carbon pipe grafting amount is 1%, 2.5%, 5%, 7.5%Elongation at break and fracture strength with the modification butadiene rubber of 10% reversible crosslink.
Table 2
| Carbon pipe addition (%) | 0 | 1 | 2.5 | 5 | 7.5 | 10 |
| Fracture strength (MPa) | 3.10 | 17.29 | 18.71 | 20.03 | 16.4 | 15.22 |
| Elongation at break (%) | 1109.6 | 780.8 | 738.8 | 705.8 | 584.2 | 535.3 |
Embodiment 3
Composite after moulding is immersed in dimethylbenzene, is heated to 150 DEG C, now material dissolves, shouldSolution is poured on glass plate, and film forming has completed the recycling of moulding again. Taking furans percent grafting as 20%, carbon is receivedMitron addition is that 10% composite is example, carries out altogether three times and repeats moulding, and stress-strain diagram is shown in Fig. 4. MaterialMaterial at every turn after moulding again, fracture strength, elongation at break modulus all declines to some extent, think be due toWhen each high temperature solution is crosslinked, there is being cross-linked between a small amount of residual carbon pipe and polymer not untie completely, cause againThe degree of cross linking of the material of moulding declines, therefore several parameter all declines to some extent. But it still has good mechanical property.
Those skilled in the art it should be noted in the discussion above that embodiment described in the invention is only exemplary, can beIn scope of the present invention, make various other replacements, changes and improvements. Thereby, the invention is not restricted to above-mentioned embodiment,And be only defined by the claims.
Claims (8)
1. a carbon nano-tube modification thermoplastic elastomer composite material with solvent resistance, is characterized in that, this is compoundMaterial is composited by modified thermoplastic elastomer and CNT, percentage meter by weight, the modification in compositeThermoplastic elastomer (TPE) accounts for 90-99%, and CNT accounts for 1-10%; Wherein: described modified thermoplastic elastomer is that furans connectsThe unsaturated thermoplastic elastomer (TPE) of branch modification.
2. carbon nano-tube modification thermoplastic elastomer composite material according to claim 1, is characterized in that: unsaturatedThermoplastic elastomer (TPE) is the styrene analog thermoplastic elastomer that molecule includes unsaturated double-bond.
3. carbon nano-tube modification thermoplastic elastomer composite material according to claim 1, is characterized in that: modification heatIn thermoplastic elastic, the graft ratio of furans is 5%～50%.
4. according to the carbon nano-tube modification thermoplastic elastomer composite material described in claim 1 or 3, it is characterized in that: changeIn thermoplastic elastic hot in nature, the graft ratio of furans is 10%～30%.
5. carbon nano-tube modification thermoplastic elastomer composite material according to claim 1, is characterized in that: carbon nanometerPipe is SWCN or multi-walled carbon nano-tubes.
6. a preparation method with the carbon nano-tube modification thermoplastic elastomer composite material of solvent resistance, its feature existsIn, it is by being dispersed in modified thermoplastic elastomer and CNT dissolving in organic solvent, and heating, stirsAfter, high temperature film forming prepares; In the composite obtaining, percentage meter by weight, modified rubber accounts for 90-99%;CNT accounts for 1-10%.
7. preparation method according to claim 6, is characterized in that, described organic solvent be selected from benzene, dimethylbenzene,Toluene, alcohols, chloroform, carrene, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide (DMSO), N, N '-dimethyl formamide, N, N '-Any in dimethylacetylamide or ketone.
8. preparation method according to claim 6, is characterized in that, heating-up temperature is 60-130 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108329645A (en) * | 2018-02-01 | 2018-07-27 | 上海交通大学 | A kind of hybrid material of UV light-induced gradient-structure, preparation method and its application in terms of response transfer of shapes |
| CN110650838A (en) * | 2017-05-15 | 2020-01-03 | 加拿大国家研究理事会 | Stretchable nanocomposite skin materials and related structures |
| CN111900273A (en) * | 2020-07-16 | 2020-11-06 | 惠州市吉昀精密部件有限公司 | Heat-dissipation waterproof composite lithium ion battery shell material and preparation method thereof |
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| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
| CN104628895A (en) * | 2015-01-27 | 2015-05-20 | 上海交通大学 | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material |
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| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
| CN104628895A (en) * | 2015-01-27 | 2015-05-20 | 上海交通大学 | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material |
| CN105254963A (en) * | 2015-10-31 | 2016-01-20 | 上海交通大学 | Recyclable carbon nano-tube modified rubber composite material, preparation method and remodeling recycling method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110650838A (en) * | 2017-05-15 | 2020-01-03 | 加拿大国家研究理事会 | Stretchable nanocomposite skin materials and related structures |
| US11744924B2 (en) | 2017-05-15 | 2023-09-05 | National Research Council Of Canada | Stretchable nanocomposite skin material and related structures |
| CN108329645A (en) * | 2018-02-01 | 2018-07-27 | 上海交通大学 | A kind of hybrid material of UV light-induced gradient-structure, preparation method and its application in terms of response transfer of shapes |
| CN108329645B (en) * | 2018-02-01 | 2020-06-09 | 上海交通大学 | Hybrid material with ultraviolet light induced gradient structure, preparation method and application of hybrid material in responsive shape transformation |
| CN111900273A (en) * | 2020-07-16 | 2020-11-06 | 惠州市吉昀精密部件有限公司 | Heat-dissipation waterproof composite lithium ion battery shell material and preparation method thereof |
| CN111900273B (en) * | 2020-07-16 | 2022-09-23 | 惠州市吉昀精密部件有限公司 | Heat-dissipation waterproof composite lithium ion battery shell material and preparation method thereof |
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